Transient analysis of alkaline anion exchange membrane fuel cell anode

Alkaline anion exchange membrane (AAEM) fuel cell has attracted increasing attention in recent years due to its several outstanding advantages over proton exchange membrane (PEM) fuel cell such as fast electrochemical kinetics and friendly alkaline environment for catalysts. In this study, a three-dimensional (3D) half-cell transient model is developed to study the dynamic characteristics of AAEM fuel cell under different step changes of operating conditions. It is found that the current density has significant effects on the distribution of liquid water, while the anode stoichiometric ratio effect is insignificant. More time is needed to reach a steady state when the current density decreases rather than increases, and the similar phenomenon also occurs when the operating temperature decreases rather than increases, however, this effect within a low temperature range becomes insignificant. Moreover, the overshoot and undershoot of water diffusion through membrane can also be observed with the step change of the anode stoichiometric ratio and anode inlet relative humidity. The model prediction also has reasonable agreement with published experimental data. The dynamic behaviors observed in this study are of significant importance to the development of AAEM fuel cells for portable and automotive applications.     

Water management in alkaline anion exchange membrane fuel cell anode

Water management is an important issue for alkaline anion exchange membrane fuel cell (AAEMFC) due to its significant role in the energy conversion processes. In this study, a numerical model is developed to investigate the water transport in AAEMFC anode. The gas and liquid transport characteristics in the gas diffusion layer (GDL) and catalyst layer (CL) with different designs and under various operating conditions are discussed. The results show that the current density affects the liquid water distribution in anode most significantly, and the temperature is the second considerable factor. The stoichiometry ratio of the supplied reactant has insignificant effect on the liquid water transport in anode. The change of liquid water amount in anode with cathode relative humidity follows a similar trend with anode inlet relative humidity. Some numerical results are also explained with published experimental and modeling data with reasonable agreement.     

Study of operating conditions and cell design on the performance of alkaline anion exchange membrane based direct methanol fuel cells

Direct methanol fuel cells using an alkaline anion exchange membrane (AAEM) were prepared, studied, and optimized. The effects of fuel composition and electrode materials were investigated. Membrane electrode assemblies fabricated with Tokuyama^® AAEM and commercial noble metal catalysts achieved peak power densities between 25 and 168 mW cm⁻² depending on the operating temperature, fuel composition, and electrode materials used. Good electrode wettability at the anode was found to be very important for achieving high power densities. The performance of the best AAEM cells was comparable to Nafion^®-based cells under similar conditions. Factors limiting the performance of AAEM MEAs were found to be different from those of Nafion^® MEAs. Improved electrode kinetics for methanol oxidation in alkaline electrolyte at Pt-Ru are apparent at low current densities. At high current densities, rapid CO₂ production converts the hydroxide anions, necessary for methanol oxidation, to bicarbonate and carbonate: consequently, the membrane and interfacial conductivity are drastically reduced. These phenomena necessitate the use of aqueous potassium hydroxide and wettable electrode materials for efficient hydroxide supply to the anode. However, aqueous hydroxide is not needed at the cathode. Compared to AAEM-based fuel cells, methanol fuel cells based on proton-conducting Nafion^® retain better performance at high current densities by providing the benefit of carbon dioxide rejection.     

Two dimensional dynamic modeling of a shell-and-tube water-to-gas membrane humidifier for proton exchange membrane fuel cell

Water management is a crucial factor in determining the performance of proton exchange membrane fuel cell (PEMFC) for automotive application. The shell-and-tube water-to-gas membrane humidifier is useful for humidifying the PEMFC due to its good performance. Shell-and-tube water-to-gas membrane humidifiers have liquid water on one side of the tube wall and a dry gas on the other. In order to investigate humidifier performance, a two-dimensional dynamic model of a shell-and-tube water-to-gas membrane humidifier is developed. The model is discretized into three control volumes – shell, tube and membrane – in the cross-sectional direction to resolve the temperature and species concentration of the humidifier. For validation, the dew point temperature of the simulation result is compared with that of experimental data and shows good agreement with only a slight difference. The distribution of humidification characteristics can be captured using the discretization along the air-flow direction. The humidification performance of two different flow configurations, counter and parallel, are compared under various operating conditions and geometric parameters. Finally, the dynamic response of the humidifier at the step-change of various air flow rates is investigated. These results suggest that the model can be used to optimize the inlet flow humidity of a PEMFC.     

A polytetrafluoroethylene-quaternary 1,4-diazabicyclo-[2.2.2]-octane polysulfone composite membrane for alkaline anion exchange membrane fuel cells

The quaternary 1,4-diazabicyclo-[2.2.2]-octane (DABCO) polysulfone (QDPSU) was synthesised. A thin (30 μm) composite membrane based on polytetrafluoroethylene (PTFE) and QDPSU was obtained by impregnation method of QDPSU solution in PTFE support. SEM images revealed a dense and homogenous structure of PTFE-QDPSU membrane. The PTFE-QDPSU composite membrane showed good mechanical strength (a 32 MPa maximum load), and a water uptake of 61 ± 3% and a 17 ± 2% swelling degree. An ionic conductivity of 0.051 S cm⁻¹ was achieved at 50 °C and 100% RH. Preliminary data of a single MEA gave power outputs of 146 and 103 mW cm⁻² with oxygen and air respectively.     

Direct ethanol fuel cells using an anion exchange membrane

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm⁻² to 58 mW cm⁻² at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.     

质子交换膜燃料电池的多尺度传热传质

介绍了目前质子交换膜燃料电池(PEMFC)在膜、电极、单电池、电堆或系统等四个结构尺度上的传热传质过程研究;主要讨论了PEMFC内的多组分传输、膜内水管理和多孔电极内的传热、传质过程;认为建立在孔尺度水平的研究方法是深入探讨电池内多孔材料微结构传热传质的有效途径;多维、多尺度模型的建立及其模拟计算能准确反映PEMFC内部的传递过程机理,为进一步优化电池结构和操作条件提供有价值的参考。     

Effect of operating parameters on dynamic response of water-to-gas membrane humidifier for proton exchange membrane fuel cell vehicle

An analytic multi-dimensional dynamic model of a membrane type humidifier has been developed for the study of transient responses of the humidifier under proton exchange membrane fuel cell vehicle operating conditions. The dynamic responses of heat and mass transfer and fluid flow in a membrane humidifier are mathematically formulated and modeled with a newly developed pseudo-multi-dimensional concept. The model is used to analyze the performance of the humidifier under various operating conditions and the dynamic response of the humidifier under transient operating conditions. The simulation results show that, in the case of the water-to-gas type membrane humidifier modeled in this study, the time constant of water diffusion in the membrane is less than 1 s. Thus, the delay of the response of the humidifier induced by the vapor diffusion in the membrane is not significant in vehicle operation. However, it is also found that the dynamic behavior is mainly due to the thermal resistance and heat capacity of the membrane humidifier.     

Quantifying water transport in anion exchange membrane fuel cells

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.     

Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics and methanol crossover, which are limiting the development of direct methanol fuel cells. In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole), was prepared through polycondensation, grafting and quaternization. The ionic conductivity of as-synthesized anion exchange membrane can reach up to 2.79 × 10⁻² S/cm at 70 °C. The physical and chemical stability of the anion exchange membranes could also meet the requirement for alkaline direct methanol fuel cells.     

Transient two-dimensional model of heat and mass transfer in a PEM fuel cell membrane

In the present work, a numerical study of heat and mass transfer within the membrane of a proton exchange membrane fuel cell is presented. The electrolyte membrane is considered an isotropic porous medium and ideal insulator for electrons and reactants. The adopted model in this study is based on the assumption of single-phase and multi-spices flow, supposed two-dimensional and unsteady. For the water transport, the major considered forces are; the convective force, resulting from the pressure gradient, the osmotic force, due to the concentration gradient and the electric force caused by the proton migration from the anode to the cathode. Based on a one-dimensional model, found in the literature, a transient two-dimensional one was proposed. The set of governing equations, written in velocity–pressure formulation, is solved by the implicit finite difference method. An alternating Direct Implicit scheme was used for the calculation. The numerical resolution gives the time- and space-dependent temperature and water concentration. The main focus lies on the influence of different cases of boundary conditions on water concentration and heat transfer variation with the intention of testing the reliability of the proposed computational fluid dynamic (CFD) code.     

ZrO2 incorporated polysulfone anion exchange membranes for fuel cell applications

Novel imidazolium functionalized polysulfone (ImPS) membranes modified with zirconia (ZrO₂) were synthesized through solution casting technique. Structural, morphological, thermal and mechanical analysis of the composite membranes confirmed adhesion and property enhancement caused by ZrO₂. Water absorption investigations revealed better water absorption of the ImPS/ZrO₂ membranes with intact morphology. Maximum ion exchange capacity and ionic conductivity for the composite membranes were obtained as 2.84 mmol/g and 80.2 mS/cm (50 ^°C) which was 21% and 47% higher as compared to pure ImPS membrane. Alkaline stability of the blend membranes was increased due to strong interaction between ZrO₂ and ImPS molecules. Fuel cell performance using Pt/C catalysts exhibited OCP and power density elevation with incremental amounts of ZrO₂ in the composite membrane composition. ImPS membrane with 10% ZrO₂ recorded a highest OCP and power density of 1.04 V and 270 mW/cm² which was 35% and 39% higher than the pure ImPS. Thus, the anion exchange membranes developed by ImPS/ZrO₂ blending could be suiting well for alkaline fuel cells applications.     

Water management in an alkaline fuel cell

Alkaline fuel cells are low temperature fuel cells for which stationary applications, like cogeneration in buildings, are a promising market. To guarantee a long life, water and thermal management has to be controlled in a careful way. To understand the water, alkali and thermal flows, a model for an alkaline fuel cell module is developed using a control volume approach. Special attention is given to the physical flow of hydrogen, water and air in the system and the diffusion laws are used to gain insight in the water management. The model is validated on the prediction of the electrical performance and thermal behaviour. The positive impact of temperature on fuel cell performance is shown. New in this model is the inclusion of the water management, for which an extra validation is performed. The model shows that a minimum temperature has to be reached to maintain the electrolyte concentration. Increasing temperature for better performance without reducing the electrolyte concentration is possible with humidified hot air.     

Preparation and performance of bisimidazole cationic crosslinked addition-type polynorbornene-based anion exchange membrane

The late transition metal catalyst system (η³-allyl)Pd(PPh₃)Cl/Li[B(C₆F₅)₄]·2.5Et₂O (Li[FABA]) was used to catalyze 5-norbornene-2-methylenehexyl ether (NB-MHE) and 5-norbornene-2-methylene-(6-bromohexyl) ether (NB–O–Br) controllable addition copolymerization to obtain post-functionalized vinyl addition-type block copolymer aP(NB-O-Br-b-NB-MHE). 1,6-Bis(2-methylimidazole)hexane (Bis-MeIm) was used as a crosslinking agent to prepare a series of anion exchange membranes (AEMs) CL-aP(NB-O-Br-b-NB-MHE). The initial thermal decomposition temperature of the obtained addition-type polynorbornene-based AEM was about 250 °C. The AEM had moderate water uptake (WU) and swelling ratio (SR), and obvious micro-phase separation structure that could be observed from the AFM phase diagram. It could maintain high OH^? conductivity (85.07 mS cm^?1, 80 °C) and alkali resistance stability (soaking alkali for more than 500 h at 25 °C). In the single cell test of the H₂/O₂ fuel cell assembled by CL5-aP(NB-O-Br-b-NB-MHE), the peak power density was 177 mW cm^?2.     

Radiation grafted membranes for superior anion exchange polymer membrane fuel cells performance

A study of radiation grafted polymers on the conductivity and performance of alkaline anion exchange membrane fuel cells (AAEMFCs) is reported. The aminated poly (LDPE-g-VBC), poly (HDPE-g-VBC) and poly (ETFE-g-VBC) membranes were produced by the using the radiation grafting technique. Differences in grafting behaviour are observed between the studied materials caused by differences in the base polymer film properties as molar mass, crystallinity, orientation or grafting technique used. In plane conductivities increased with Degree of Grafting DoG. At a DoG of 68% the LDPE-g-VBC membrane achieved an in-plane ionic conductivity between 0.18 and 0.32 S cm⁻¹ in the temperature range 20–80 °C. Measured through plane conductivities were lower than that of the in plane ones for all studied membranes. Membranes with the highest degree of swelling showed the highest through plane conductivity of 0.07–0.11 S cm⁻¹. The membrane specific resistance (per MEA cm²) of most of the produced membranes was in the range of 0.09–0.18 Ω cm². While membrane conductivity and hence IR loss is a crucial factor in fuel cell performance, membrane water permeability is a similarly crucial key for optimised water transport to the cathode. The main source of performance loss of AAEMFCs is believed to be restricted mass transport of water to the cathode reaction sites. The highly humidified anode stream along with large amount of water produced at the anode at high current densities could lead to flooding if water is not removed quickly to the cathode via the membrane (back diffusion) where it is consumed.     

Electrochemical and fuel cell evaluation of Co based catalyst for oxygen reduction in anion exchange polymer membrane fuel cells

Co based catalyst were evaluated for oxygen reduction (ORR) in liquid KOH and alkaline anion exchange membrane fuel cells (AAEMFCs). In liquid KOH solution the catalyst exhibited good performance with an onset potential 120 mV more negative than platinum and a Tafel slope of ca. 120 mV dec⁻¹. The hydrogen peroxide generated, increased from 5 to 50% as the electrode potential decreased from 175 to −300 mV vs. SHE.In an AAEMFC environment, one catalyst (GP2) showed promising performance for ORR, i.e. at 50 mA cm⁻² the differences in cell potential between the stable performance for platinum (more positive) and cobalt cathodes with air and oxygen, were only 45 and 67 mV respectively. The second catalyst (GP4) achieved the same stable power density as with platinum, of 200 and 145 mW cm⁻², with air at 1 bar (gauge) pressure and air (atm) cathode feed (60 °C), respectively. However the efficiency was lower (i.e. cell voltage was lower) i.e. 40% in comparison to platinum 47.5%.     

Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Preparation of polytetrafluoroethylene porous membrane based composite alkaline exchange membrane with improved tensile strength and its fuel cell test

A strategy to improve the alkaline exchange membrane tensile strength was introduced based on porous PTFE and quaternized polyvinyl benzyl chloride (qPVBz/OH⁻). A thin PTFE film was used as the support to prepare the composite AAEM to improve the mechanical strength. Tensile stress tests showed 51.1 MPa which was twice that of the pure anion exchange membrane qPVBz/OH⁻. SEM observations showed that the pores of the PTFE were successfully filled with qPVBz/OH⁻ polymer and there was no structure defects in the cross-section of the resultant membrane. The synthesized composite membrane had very good thermal stability. The through plane ionic conductivity was in the range of 1.65 × 10⁻² to 2.2 × 10⁻² S cm⁻¹ in the temperature range of 25 °C–60 °C. The power density of H₂ and O₂ fuel cell gave 162 mW cm⁻².     

The effect of electrode parameters on the performance of anion exchange polymer membrane fuel cells

An investigation of several electrode parameters on performance of an alkaline membrane fuel cell is described. The studied parameters were: ionomer content, anode and cathode catalyst layer thickness, electrode aminating agent and membrane thickness.It was found that an optimum ionomer content depended on a balance between the OH⁻ ion/water mobility and the oxygen solubility/diffusivity through it and which varied with temperature. Thick catalyst layers were necessary for the anode as thin anode catalyst layers suffered from flooding. 40%Pt/C provided the best thickness (with loading of 0.4 mg_Pt cm⁻²) for cathodes operating with air.An aminated low density poly(ethylene-co-vinyl benzyl chloride) (LDPE-VBC) membrane was shown to be a good membrane for an alkaline membrane fuel cell, giving conductivities up to 0.13 S cm⁻¹ at 80 °C. A Membrane Electrode Assembly (MEA) utilizing this membrane with fully hydrated thickness of 57 μm produced good peak power density, at a high potential of 500 mV, of 337 mW cm⁻² with air (1 bar gauge) at 60 °C.     

Preparation and characterization of imidazolium-based membranes for anion exchange membrane fuel cell applications

New anion exchange membranes (AEMs) with high conductivity, good dimensional and alkaline stability are currently required in order to develop alkaline fuel cells into efficient and clean energy conversion devices. In this study, a series of AEMs based on 1, 2-dimethyl-3-(4-vinylbenzyl) imidazolium chloride ([DMVIm][Cl]) are prepared and investigated. [DMVIm][Cl] is synthesized and used as ion carriers and hydrophilic phase in the membranes. The water uptake, swelling ratio, IEC and conductivity of the AEMs increase with increasing the [DMVIm][Cl]. The imidazolium-based AEMs show excellent thermal stability, sufficient mechanical strength, the membrane which containing 30% mass fraction of [DMVIm][Cl] shows conductivity up to 1.0 × 10^?2 S cm^?1 at room temperature and good long-term alkaline stability in 1 M KOH solution at 80 °C. The results of this study suggest that this type of AEMs have good perspectives for alkaline anion exchange membrane fuel cell applications.